JPH06102722B2 - Polyether Copolymer Having Antioxidant Group in Side Chain - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyether copolymer useful as an oil resistant rubber material.

(Problems to be solved by the prior art and the invention) In order to suppress the oxidative deterioration of the rubber material, an antioxidant is usually added, but in the environment of oil, the antioxidant is separated from the rubber material by extraction. In many cases, the antioxidant effect is reduced due to volatilization and surface migration of the antioxidant at high temperatures. In addition, such behavior of the antioxidant leads to a decrease in heat resistance of the rubber material.

As one of the methods for preventing this, it is conceivable to copolymerize a monomer having a group having an antioxidant action so that the side chain of the polymer holds the antioxidant group as a pendant.
However, such copolymers have not been found so far for various polyether rubbers including epichlorohydrin rubber which is an oil resistant rubber.

As a monomer expected to give such a copolymer, T. Fujisawa et al. 4-hydroxy-3,5-di-t
-Butylphenylglycidyl thioether has been reported (T. Fujisawa et al., JP-olym.Sci., Part B 12 , 577 (197
4)) However, the polymerization reaction of this monomer does not proceed at all even when a diethylzinc-water catalyst which gives a high polymer of an epoxy compound is used. It is considered that one of the causes is that the thioether group or the sterically hindered phenolic hydroxyl group inhibits the high polymerization reaction.

In addition, the above-mentioned thioether monomer uses a large amount of zinc dust in the production of 4-mercapto-3,5-di-t-butylphenol, which is the starting material for its synthesis. It is as low as 35% and is not industrially useful.

(Means for Solving the Problems) In view of the above points, the inventors of the present invention have made extensive studies for the purpose of obtaining a polyether polymer having an antioxidant phenol group in a side chain. As a result, they have found that a polyether copolymer containing a structural unit represented by the following formula (I) as an essential component can sufficiently achieve the above object, and completed the present invention.

The present invention includes a repeating unit of the following formula (I) and the following general formula (II) (Wherein, R represents _{group: H, -CH 3, -CH 2} Cl, -CH 2 Br, -CH 2 OCH
₂ CH = CH ₂ or _{-CH 2 OCOC n H 2n + 1} (n is an integer from 1 to 4) indicating the. ) 1 or 2 or more of the repeating units represented by the formula (1) / (II) = 0.1 to 3 in mol% as a monomer composition ratio.
0 / 99.9 to 70, and a reduced viscosity measured with a 0.1 g / dl monochlorobenzene solution at 80 ° C. is 0.4 to 10 and a polyether copolymer having an antioxidant phenol group in the side chain. Is.

The novel copolymer of the present invention is 4-hydroxy-3,5-di-t-butylphenyl glycidyl ether represented by the following formula (I ') (a novel compound according to the applicant's application. And the presence of a catalyst, which is a condensation product of an organotin compound and a phosphoric acid alkyl ester, with one or more monomers of an epoxide represented by the following general formula (II '). It can be obtained by polymerizing below.

(Wherein, R represents _{group: -H, -CH 3, -CH 2} Cl, -CH 2 Br, -CH 2
OCH ₂ CH = CH ₂ or -CH ₂ OCOC _n H _{2n + 1} (n is an integer of 1 to 4)
Indicates. ) The structural units (I) and (II) (II-1 to 6) of the present invention are
As shown below, epoxides (I ') and (II') (I
It is introduced by the ring opening of I'-1 to 6).

Specific examples of the epoxide (II′-1) include glycidyl acetate and glycidyl propionate.

The composition of the polyether copolymer of the present invention in terms of monomer is (I) / (II) = 0.1 to 30 / 99.9 to 70 in mol%,
The following composition ratio (mol%) depending on the type of structural unit (II)
Are more preferably used. When (I) is less than 0.1, the antioxidant effect is low. Further, when it exceeds 30, not only the antioxidant effect is not improved, but the original properties of the polyether are impaired.

1) (I) / (II-1) / (II-2) = 0.1 to 2/88 to 98.
9 / 1-10 When (I) is less than 0.1, the antioxidant effect is low, and (I) is 2
Even if it exceeds, there is no improvement in the antioxidant effect. (II-2) is 1
When it is less than 10, the vulcanization effect is low, and when (II-2) exceeds 10, not only the aging property is deteriorated but also a tendency of gelation appears.

2) (I) / (II-1) / (II-3) = 0.1 to 2/96 to 99.
4 / 0.5-2 When (I) is less than 0.1, the antioxidant effect is low, and (I) is 2
Even if it exceeds, there is no improvement in the antioxidant effect. (II-3) is 0.
When it is less than 5, the vulcanization effect is low, and when (II-3) exceeds 2, corrosive properties are exhibited.

3) (I) / (II-2) / (II-4) = 0.1-4 / 2-10 / 8
6-97.9 (I) is less than 0.1, the antioxidant effect is low, and (I) is 4
Even if it exceeds, there is no improvement in the antioxidant effect. (II-2) is 2
When it is less than 10, the vulcanization effect is low, and when (II-2) exceeds 10, not only the aging property is deteriorated but also a tendency of gelation appears.

4) (I) / (II-3) / (II-4) = 0.1-5 / 0.5-3 /
92-99.4 (I) is less than 0.1, the antioxidant effect is low, and (I) is 5
Even if it exceeds, there is no improvement in the antioxidant effect. (II-3) is 0.
If it is less than 5, the vulcanization effect is low, and if (II-3) exceeds 3, corrosive properties are exhibited.

5) (I) / (II-5) = 0.1 to 30/70 to 99.9 If (I) is less than 0.1, the antioxidant effect is low and (I) is 30.
If it exceeds, cold resistance is deteriorated, and aging resistance becomes a problem.

6) (I) / (II-2) / (II-5) = 0.1 to 3/1 to 10/8
7-98.5 (I) is less than 0.1, the antioxidant effect is low, and (I) is 3
Even if it exceeds, there is no improvement in the antioxidant effect. (II-2) is 1
If it is less than 1, the aging property will be deteriorated, and the sulfur vulcanizability will be deteriorated. If (II-2) is more than 10, the aging property will be deteriorated.

7) (I) / (II-4) / (II-5) = 0.1-5 / 20.1-6
0/35 to 74.9 (I) is less than 0.1, the antioxidant effect is low, and (I) is 5
Even if it exceeds, there is no improvement in the antioxidant effect. (II-4) is 2
If it is less than 0.1, the cold resistance decreases, and if (II-4) exceeds 60, the oil resistance decreases.

8) (I) / (II-5) / (II-6) = 0.1 to 3/20 to 74.
9 / 25-79.9 (I) is less than 0.1, the antioxidant effect is low, and (I) is 3
Even if it exceeds, there is no improvement in the antioxidant effect. (II-6) is 25
If it is less than the following, cold resistance is deteriorated, and if (II-6) exceeds 79.9, heat resistance and water resistance become problems.

9) (I) / (II-2) / (II-5) / (II-6) = 0.
1 to 3/1 to 3/20 to 73.9 / 25 to 78.9 When (I) is less than 0.1, the antioxidant effect is low and (I) is 3
Even if it exceeds, there is no improvement in the antioxidant effect. (II-2) is 1
If it is less than 3 or more than 3, problems occur in aging. (II-
If 6) is less than 25, the cold resistance decreases, and if (II-6) exceeds 73.9, problems arise in heat resistance and water resistance.

10) (I) / (II-2) / (II-4) / (II-6) = 0.
1 to 2/1 to 4/40 to 83.9 / 15 to 58.9 When (I) is less than 0.1, the antioxidant effect is low and (I) is 2
Even if it exceeds, there is no improvement in the antioxidant effect. (II-2) is 1
If it is less than 4, the vulcanization effect is low, and if (II-2) exceeds 4, problems occur in heat resistance and oil resistance. When (II-6) is less than 15, oil resistance is reduced, and when (II-6) exceeds 58.9, water resistance is reduced.

11) (I) / (II-2) / (II-3) / (II-4) /
(II-6) = 0.1 to 3/1 to 5/1 to 4/40 to 82.9 / 15 to 57.9 When (I) is less than 0.1, the antioxidant effect is low and (I) is 3
Even if it exceeds, there is no improvement in the antioxidant effect. (II-2) is 1
If it is less than 2, the sulfur vulcanizability is low with a problem in aging property, and if (II-2) is more than 5, the aging property is inferior and the oil resistance is lowered. If (II-3) is less than 1, the vulcanizability is lowered, and if (II-3) is more than 4, there is a problem in corrosiveness. If (II-6) is less than 15, the cold resistance decreases,
When (II-6) exceeds 57.9, heat resistance and water resistance are reduced.

The condensation product, which is the polymerization catalyst, is a thermal condensate of a specific organotin compound (A) and a phosphoric acid alkyl ester (B) described in US Pat. No. 3,773,694 of the present applicant. Therefore, it is extremely effective for the synthesis of the copolymer of the present invention.

The organotin compound (A) is a compound selected from the following general formulas (i) to (iv).

R ¹ _a S _n X _4-a (i) (In the formula (i), R ¹ is an optionally substituted alkyl group having 1 to 12 carbon atoms, alkenyl group, cycloalkyl group, aryl A group selected from the group of groups and aralkyl groups, X is an atom or group selected from the group of halogen atoms, alkoxy groups, aryloxy groups, acyloxy groups and partial ester residues of phosphoric acid, and a is 1 to 4 R is the same or different when a is 2 or more, and X may be the same or different when a is 1 or 2.) R ¹ _b S _n O _c (ii) (However, in the formula (ii), R ¹ is the same as R ^{1 in the} formula (i). B is 1 or 2, and when b is 1, c is 3 /
2 and c is 1 when b is 2. Further, the compound of formula (ii) may form a complex with the compound of formula (i). ) R ² R ¹ ₂ S _n OS _n R ¹ ₂ R ² (iii) (However, in the formula (iii), R ¹ is R ^{1 in the} formula (i).
And R ² is the same as R ¹ or X in the formula (i). Two R ² may be the same or different. ) (R ² ₃ S _n ) _d X ¹ (iv) (However, in the formula (iv), R ² is R ^{2 in the} formula (iii).
And at least one is a group selected from R ^{1 in the} formula (i). X ¹ is a group selected from the group consisting of a carbonic acid group, an oxygen acid group of phosphorus, a partial ester residue of phosphoric acid, a polybasic carboxylic acid group, and a polyhydric alcohol residue. d is a number greater than 1 corresponding to the basicity of X ¹ . The following may be mentioned as specific examples of the organotin compound (A) represented by the above formulas (i) to (iv).

The compounds belonging to general formula (i) include (C ₂ H ₄ ) ₄ Sn, (C ₆ H ₅ ) ₄ Sn, (CH ₃ ) ₃ SnF, (C ₄ H ₉ ) ₃ SnCl, (C
_{H 3) 3 SnBr, (C} 8 H 17) 3 SnCl, (CH 3) 2 SnF 2, (C 4 H 9) 2 SnCl 2,
(C ₁₂ H ₂₃ ) ₂ SnBr ₂ , (Cyclo-C ₆ H ₁₁ ) ₂ SnI ₂ , (C ₄ H ₉ ) SnF ₃ , and (C
₈ H ₁₇ ) SnCl ₃ , _{(C 8 H 17) 3 SnOCOCH} 3, (C 8 H 17) 2 Sn (OCOC 17 H 35) 2, And so on.

The compounds belonging to the general formula (ii) include (CH ₃ ) ₂ SnO, (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO, (C ₆ H ₅ ) ₂ SnO, CH
₃ SnO _3/2 , C ₄ H ₉ SnO _{3/2, and the} like, and examples of complexes of the compounds of the general formula (i) and the general formula (ii) include (CH ₃ ) ₂ SnO. (C ₂ H _{5) 2} SnBr _2, and the like _{(CH 3) 2 SnO · (} CH 3) 2 SnCl 2.

Examples of the compound belonging to the general formula (iii) include (CH ₃ ) ₃ SnOSn (CH ₃ ) ₃ , Cl (C ₄ H ₉ ) ₂ SnOSn (C ₄ H ₉ ) Cl, (CH ₃ CO _{3
O) (C 6 H 5)} 2 SnOSn (C 6 H 5) 2 (CH 3 COO) , and the like.

The compounds belonging to general formula (iv), [(CH _{3) 3} Sn] ₂ CO _3, [(C ₄ H _{9) 3} Sn] _{2 CO 3, (C 4 H} 9) 3 SnOP
_{(O) (OC 8 H 17} ) 2, [(C ₈ H _{17) 3} Sn] _{3 PO 4, (C 4 H} 9) 3 SnOCH 2 CH 2
OSn (C ₄ H ₉ ) ₃ , And so on.

As the phosphoric acid alkyl ester (B) which is another component constituting the catalyst, a complete or partial ester of orthophosphoric acid represented by the following general formula (III) is preferably used.

(R ³ O) ₃ P = O (III) (In the formula (III), R ³ is hydrogen or an alkyl group having 2 or more carbon atoms, an alkenyl group or a cycloalkyl group, and at least one of R ³ Is a group other than a hydrogen atom.) Specific examples of the above formula (III) include (C ₂ H ₅ ) ₃ PO ₄ , (C ₃ H ₇ ) ₃ PO ₄ , and (C ₄ H ₉ ) _3. PO ₄ , (C ₈ H ₁₇ ) ₃ PO ₄ ,
(CH ₂ = CH-CH ₂ ) ₃ PO ₄ , (C ₆ H ₁₁ ) ₃ PO ₄ , (ClCH ₂ -CH ₂ ) ₃ PO ₄ , (C
l ₂ C ₃ H ₅ ) ₃ PO ₄ , (C ₂ H ₅ ) ₂ HPO ₄ , (C ₄ H ₉ ) ₂ HPO ₄ , (C ₄ H ₉ ) H ₂ PO ₄
And so on.

The catalyst is obtained as a condensation product by heating a mixture of the organotin compound (A) and the phosphoric acid alkyl ester (B) in the temperature range of 150 to 300 ° C. The solvent may be used if necessary. Component (A) and (B)
Ingredients are usually contained in a ratio of tin atoms to phosphorus atoms of 1:10 to 1
It is used in the range of 0: 1.

In the catalyst formation reaction, various relatively simple substances are formed and eliminated by the condensation reaction according to the types of the component (A) and the component (B). The obtained condensate exhibits the desired activity at various stages of the degree of condensation.

The optimum condensation degree varies depending on the types and ratios of the component (A) and the component (B), but they can be easily determined experimentally. The condensate is generally soluble in a solvent such as hexane or benzene at the initial stage, but becomes insoluble as the condensation reaction proceeds.

The polyether copolymer of the present invention is a compound of formula (I ') 4-hydroxy-3,5-di- (I') using the condensation product as a catalyst.
The t-butylphenyl glycidyl ether and the other epoxide (II ′) are usually stirred or shaken at 0 to 80 ° C. in the presence or absence of a solvent such as an aliphatic hydrocarbon or an aromatic hydrocarbon. It is obtained by polymerizing. The amount of the catalyst used is appropriately in the range of 0.01 to 5.0 g based on 1 mol of the total raw material monomer. It is desirable that the water content of the reaction system during the reaction be as low as possible.

The polyether copolymer of the present invention has a concentration of 0.1 g / d at 80 ° C.
A rubber material having a reduced viscosity in the range of 0.1 to 10 measured with a monochlorobenzene solution of 1 has good usability as a rubber material.

(Example) Example 1 10.0 g of dibutyltin oxide and 23.4 g of tributyl phosphate were placed in a 100 ml three-necked flask equipped with a stirrer, a thermometer and a distillation apparatus, and heated at 260 ° C for 15 minutes while stirring under a nitrogen stream and distilled. The product was distilled off to obtain a solid condensed substance as a residue. The following polymerization was carried out using this as a catalyst.

The inside of a glass ampoule having an inner volume of 50 ml was replaced with nitrogen, and 54.6 mg of the above condensed substance and 4-hydroxy-3,5-di-t-
20 ml of a benzene solution containing 0.064 g of butylphenyl glycidyl ether (I '), 14.8 g of glycidyl propionate and 0.13 g of allyl glycidyl ether was charged, and after sealing the tube, the reaction was carried out at 30 ° C for 83 hours while shaking the ampoule.

After the reaction, the reaction product was poured into 100 ml of hexane, and the mixture was soaked overnight, the hexane was removed by decantation, further washed with 100 ml of hexane twice and washed with 100 ml of methanol twice, and dried under reduced pressure for 8 hours to give a rubber-like polymer. 11.2 g was obtained.

Table 1 shows the charged monomer ratio, the reaction conditions, the composition ratio of each component of the produced polymer, and the reduced viscosity. The composition ratio was determined by measuring the ultraviolet absorption spectrum and iodine value. The reduced viscosity is a value measured at 80 ° C. in a 0.1 g / dl chlorobenzene solution.

The NMR spectrum of the obtained copolymer was as follows. ¹ H-NMR (CDCl ₃ ) δ (ppm) 1.1 to 1.2 (-CH ₃ (II-1)), 1.42 (t-butyl (I)), 2.3 to 2.4 (-CH ₂ (II-1)), 3.5 to 3.7 _{3.8~4.2 (-O-CH 2 - (} II-2)), 4~4.3 (-O-CH
_{2 - (II-1))} , 5.1~5.3 (= CH 2 (II-2)), 5.8~
5.9 (-CH = (II-2)), 6.72 (aromatic (I)) Examples 2 to 14 Copolymerization was carried out in the same manner as in Example 1 with the charged monomers, the amount of catalyst and the reaction conditions shown in Table 1. The composition ratio and reduced viscosity of the obtained copolymer were determined in the same manner as in Example 1 and shown in Table 1.

The numerical values of ¹ H-NMR (CDCl ₃ ) δ (ppm) were as follows.

Example 2 (I / II-1 / II-2) was the same as the numerical value of Example 1.

Example 3 (I / II-1 / II-3) 1.1~1.2 (-CH 3 (II-
1)), 1.41 (t-butyl (I)), 2.3 to 2.4 (CH ₂ (II
-1)), 3.5-3.7 _{4.0~4.3 (-O-CH 2 - (} II-1)), 6.72 ( aromatic (I)) Example 4 (I / II-2 / II-4) 1.42 (t- butyl (I)), 3.2 ~ 3.6 _{3.95 (-O-CH 2 - (} II-2)), 5.1~5.3 (= CH 2 (II
-2)), 5.8 to 5.9 (-CH = (II-2)), 6.70 (aromatic (I)) Example 5 (I / II-2 / II-4), Example 6 (I / II-) 2 / II-
4) was the same as in Example 4.

Example 7 (I / II-3 / II-4) 0.9~1.2 (-CH 3 (II-
4)), 1.42 (t-butyl (I)), 3.2 to 3.6 6.74 (Aromatic (I)) Example 8 (I / II-3 / II-4) was the same as Example 7.

Example 9 (I / II-5) 1.43 (t-butyl (I)), 3.6-
3.8 6.74 (Aromatic (I)) Example 10 (I / II-5) and Example 11 (I / II-5) were the same as Example 9.

Example 12 (I / II-2 / II-5) 1.43 (t-butyl (I)), 3.6-3.8 _{4 (-O-CH 2 - (} II-2)), 5.1~5.3 (= CH 2 (II-
2)), 5.8 to 5.9 (-CH = (II-2)), 6.75 (aromatic (I)) Example 13 (I / II-4 / II-5) 1.42 (t-butyl (I)), 3.4 ~ 3.8 6.7 (Aromatic (I)) Example 14 (I / II-4 / II-5) was the same as Example 13.

Example 15 The polymerization reaction was carried out in a four-necked 3 l glass flask equipped with a stirrer, a thermometer, a sample introduction part and a nitrogen introduction part.
After replacing the inside of the reactor with nitrogen, 2.2 g of the above catalyst, 1092 g of hexane, 4
4.6 g of -hydroxy-3,5-di-t-butylphenylglycidyl ether (I '), 305 g of epichlorohydrin and 145 g of ethylene oxide were charged and reacted at 20 ° C for 10 hours while stirring.

After completion of the polymerization reaction, remove hexane and then add 2 with hexane 1.
It was washed twice and further washed with hot water to obtain a rubbery solid polymer. Table 1 shows the charged monomer ratio, the reaction conditions, the composition ratio of each component of the produced polymer, and the reduced viscosity obtained in the same manner as in Example 1. The composition ratio was determined by ultraviolet absorption spectrum and chlorine elemental analysis. The NMR spectrum of the obtained copolymer was as follows. ¹ H-NMR (CDCl ₃ ) δ (ppm) 1.41 (t-butyl (I)), 3.6 to 3.8 —CH ₂ —O— (II-6)), 6.7 (Aromatic (I)) Examples 16 to 21 Copolymerization was carried out in the same manner as in Example 15 with the charged monomers, the amount of catalyst and the reaction conditions shown in Table 1. The compositional ratio and reduced viscosity of the obtained copolymer were determined in the same manner as in Example 15 and are shown in Table 1.

The numerical values of ¹ H-NMR (CDCl ₃ ) δ (ppm) were as follows.

Examples 16, 17, and 18 (I / II-5 / II-6) were the same as Example 15.

Example 19 (I / II-2 / II-5 / II-6) 1.41 (t-butyl (I)), 3.5-3.8 _{4.0 (-CH 2 -O- (II-} 2)), 5.1~5.8 (= CH 2 (II-
2)), 5.8~5.9 (-CH = (II-2)), 6.7 ( aromatic (I)) Example 20 (I / II-2 / II-4 / II-6) 1.19 (-CH 3 ( II-
4)), 1.42 (t-butyl (I)), 3.3 to 3.7 _{-CH 2 -CH 2 -O- (II-} 6)), 4.0 (-O-CH 2 - (II
-2)), 5.1 to 5.3 (= CH ₂ (II-2)), 5.8 to 5.9 (-C
H = II-2)), 6.7 ( aromatic (I)) Example 21 (I / II-2 / II-3 / II-4 / II-6) 1.13 (-CH 3
(II-4)), 1.42 (t-butyl (I)), 3.3 to 3.7 _{-CH 2 -CH 2 -O- (II-} 6)), 4.0 (-O-CH 2 - (II
-2)), 5.1 to 5.8 (= CH ₂ (II-2)), 5.8 to 5.9 (-C
H = II-2)), 6.7 (Aromatic (I)) Example 22 40 parts of FEF carbon, sorbitan monostea with respect to 100 parts (weight basis, the same applies hereinafter) of the copolymer obtained in Example 16 above. Rate 2 parts, nickel dibutyl dithiocarbamate 1 part, calcium carbonate 5 parts, pentaerythritol (30
2 parts, 3 parts of magnesia, 1 part of 2,4,6-trimercaptotriazine and 1 part of N-cyclohexylthiophthalimide are mixed and roll-kneaded to 170 ° C.
It was vulcanized for 15 minutes. The obtained vulcanized rubber was subjected to a heat aging test at 150 ° C., and the change with time of the tensile strength change rate is shown in FIG.

Comparative Example 1 100 parts of epichlorohydrin-ethylene oxide copolymer rubber ("Epichromer C" manufactured by Daiso Co., Ltd.) was mixed with the same compounding agent as in Example 22 and roll kneading was performed, followed by addition at 170 ° C for 15 minutes. Vulcanized The obtained vulcanized rubber was subjected to a heat aging test at 150 ° C. in the same manner as in Example 22, and the change with time of the tensile strength change rate is also shown in FIG.

Example 23 A vulcanized rubber obtained in the same manner as in Example 22 was used as a fuel oil D.
Impregnated at 40 ° C for 48 hours, and after replacing with new fuel oil D, 40
After impregnation at 48 ° C for 48 hours, the rubber after impregnation was subjected to a heat aging test at 125 ° C, and the change in tensile strength with time is shown in Fig. 2.

Comparative Example 2 A vulcanized rubber obtained in the same manner as in Comparative Example 1 was used as an example.
Similar to 23, fuel oil D was impregnated at 40 ° C for 48 hours, and new fuel oil D was replaced and then impregnated at 40 ° C for 48 hours. The impregnated rubber was subjected to a heat aging test at 125 ° C, and the tensile strength was changed. The change with time of the rate is also shown in FIG.

From the test results of Example 22 and Comparative Example 1 and Example 23 and Comparative Example 2, the copolymer rubber of the present invention (I / II-5 / II-6) was obtained.
In terms of heat resistance before oil impregnation, conventional rubber (II-5 / II-
The copolymer rubber of the present invention has a performance close to that of 6) and is far superior to the rubber having only the conventional antioxidant added thereto in heat resistance after oil impregnation. I know that

(Effect of the Invention) According to the present invention, the polyether copolymer having an antioxidant group in the side chain retains the original properties of the polyether rubber, as compared with a rubber material containing a conventional antioxidant. Moreover, it has remarkably excellent oil resistance and heat aging resistance, and can be said to be industrially useful.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows the results of heat aging test of Example 22 and Comparative Example 1, and FIG. 2 shows the result of heat aging test of Example 23 and Comparative Example 2, respectively.

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Claims (1)

[Claims] 1. The following formula (I) And the following general formula (II) (Wherein, R represents _{group: H, -CH 3, -CH 2} Cl, -CH 2 Br, -CH 2 OCH
₂ CH = CH ₂ or _{-CH 2 OCOC n H 2n + 1} (n is an integer from 1 to 4) indicating the. ) 1 or 2 or more of the repeating units represented by the formula (1) / (II) = 0.1 to 3 in mol% as a monomer composition ratio.
0 / 99.9 to 70, and a reduced viscosity measured with a 0.1 g / dl monochlorobenzene solution at 80 ° C. is 0.4 to 10 and a polyether copolymer having an antioxidant phenol group in the side chain. .